EP0023728B1 - Anisotropic compounds with negative or positive direct anisotropy and limited optical anisotropy, and liquid crystal mixtures containing them - Google Patents

Anisotropic compounds with negative or positive direct anisotropy and limited optical anisotropy, and liquid crystal mixtures containing them Download PDF

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EP0023728B1
EP0023728B1 EP80200464A EP80200464A EP0023728B1 EP 0023728 B1 EP0023728 B1 EP 0023728B1 EP 80200464 A EP80200464 A EP 80200464A EP 80200464 A EP80200464 A EP 80200464A EP 0023728 B1 EP0023728 B1 EP 0023728B1
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hydrogen
carbon atoms
formula
alkyl
anisotropy
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EP0023728A1 (en
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Maged A. Dr.Ing.-Chem. Osman
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups

Definitions

  • the invention relates to new anisotropic compounds with negative or positive DK anisotropy and less, i.e. at most 0.2 optical anisotropy (An), and liquid crystal (LC) mixtures which contain these anisotropic compounds and are used as a dielectric for liquid crystal displays.
  • the anisotropic compounds known hitherto for liquid crystal mixtures whose DK anisotropy, abbreviated to DKA or ⁇ , is negative, are mostly compounds composed of two or three aromatic rings with one or two carboxyl groups and optionally a covalent bond as bridges between the rings and with one or several side groups, that is to say nuclear substituents not located in the longitudinal axis of the molecule, such as nitrile or nitro groups, as described in particular in DE-B No. 2240864, DE-A Nos. 2613293, 2835662 and 2836086.
  • Suitable methods for measuring ⁇ n are known from the literature (for example I. Haller et al. In "Mol. Cryst. And Liqu. Cryst.” 16/1972 / 53-59) and are usually based on a specific light wavelength (here 633 nm) based.
  • DE-A No. 2752975 discloses trinuclear anisotropic compounds with two or more ester bridges and one or two cyclohexyl rings in the basic structure of the molecule, which can optionally carry a side group.
  • the viscosity of the basic structure is relatively high because of the ester bridge which occurs at least twice and the side group is not considered critical.
  • DE-C No. 2752975 discloses trinuclear anisotropic compounds with two or more ester bridges and one or two cyclohexyl rings in the basic structure of the molecule, which can optionally carry a side group.
  • the viscosity of the basic structure is relatively high because of the ester bridge which occurs at least twice and the side group is not considered critical.
  • anisotropic, ie enantiotropic or monotropic or potentially liquid-crystalline compounds with a large negative DK anisotropy and small An values are required for LC displays which display the so-called inverse guest -Use host effect; furthermore, anisotropic compounds with such properties are also required for certain types of dynamic scatter cells.
  • the previously known anisotropic compounds with negative DK anisotropy do not meet the required conditions or do so to a satisfactory extent.
  • new anisotropic compounds with positive DKA and low optical anisotropy ( ⁇ n) are also required, for example for LC displays with multiplex operation.
  • the object of the invention is therefore to provide a new group of anisotropic compounds with negative or positive DKA, low optical anisotropy, low y values and reduced viscosity.
  • Compounds (1) in which two or more of the side groups X 1 to X 4 are halogen, nitro or nitrile are preferred as compounds with negative or strongly negative DKA, with nitrile being preferred.
  • halogen examples include chlorine, fluorine, bromine and iodine.
  • X 1 to X 4 act as side groups; accordingly up to three of the groups X 1 to X 4 , preferably up to two of the groups X 1 to X 4 , can also represent hydrogen atoms.
  • the compounds of the formula (1) according to the invention are also referred to below as compounds (1).
  • Preferred groups of the compounds (1) correspond to the following formulas (2) to (6):
  • At least two of the groups X 1 to X 4 are preferably halogen (preferably chlorine), nitro or nitrile, nitrile groups being particularly preferred.
  • one of the benzene nuclei of the compounds of the formulas (2) to (6) carries two halogen atoms, nitro groups or (preferably) nitrile groups.
  • Also preferred in formulas (2) to (5) is one of the bridges Z 2 , Z 3 carboxyl (-COO-) or oxycarbonyl (-OOC-) and the other is a simple covalent bond.
  • the compounds (1) can be obtained by methods known per se, e.g. by condensation of corresponding phenols or cyclohexanols with the corresponding benzoic acid or cyclohexanecarboxylic acid compounds, the respective acid component preferably in the form of a correspondingly reactive functional acid derivative, e.g. of an acid halide, in particular acid chloride, and the reaction is carried out in a liquid organic base, such as pyridine. Specific examples are given below.
  • LC mixtures according to the invention contain a component (1), e.g. in proportions of 1 to 40% by weight, or several different compounds (1) in a higher total proportion if desired.
  • LC mixtures containing at least one compound of the above formulas (2) to (6) as a component are preferred.
  • the target compound of the present example was obtained in an analogous manner from equimolar (36.5 mmol) amounts of the cyclohexane carboxylic acid compound given in Example 2 - again by converting the same with thionyl chloride into the corresponding acid chloride - and 2,3-dicyano-4-n-pentylphenol (instead of the corresponding dichlorophenol from Example 2) and workup prepared as above.
  • the target compound thus obtained is also nematic-enantiotropic and has a negative DK anisotropy and an An ⁇ 0.2.
  • the product was obtained from the organic phase by evaporating the solvent.
  • the crude product was recrystallized from ethanol for purification.
  • all of the compounds in Examples 1 to 44 also advantageously have low ⁇ n values 0 0.2 and the cyclohexane rings are each in a trans configuration.

Description

Die Erfindung betrifft neue anisotrope Verbindungen mit negativer oder positiver DK-Anisotropie und geringer, d.h. höchstens 0,2 betragender optischer Anisotropie (An), sowie Flüssigkristall(FK)mischungen, die diese anisotropen Verbindungen enthalten und als Dielektrikum für Flüssigkristallanzeigen verwendet werden.The invention relates to new anisotropic compounds with negative or positive DK anisotropy and less, i.e. at most 0.2 optical anisotropy (An), and liquid crystal (LC) mixtures which contain these anisotropic compounds and are used as a dielectric for liquid crystal displays.

Die bisher für Flüssigkristallmischungen bekannten anisotropen Verbindungen, deren DK-Anisotropie, kurz DKA oder Δε genannt, negativ ist, sind meist aus zwei oder drei aromatischen Ringen aufgebaute Verbindungen mit einer oder zwei Carboxylgruppen und gegebenenfalls einer Kovalenzbindung als Brücken zwischen den Ringen und mit einer oder mehreren Seitengruppen, d.h. nicht in der Moleküllängsachse liegenden kernständigen Substituenten, wie Nitril- oder Nitrogruppen, wie insbesondere in der DE-B Nr. 2240864, den DE-A Nrn. 2613293, 2835662 und 2836086 beschrieben. Diese bekannten anisotropen Verbindungen mit negativer DKA (Δε) haben aber hohe Viskositätswerte sowie hohe Werte der optischen Anisotropie (An); dabei ist Δε=ε"-ε┴ und Δn=n"-n┴, d.h. die DKA einer Verbindung ist negativ, wenn die Dielektrizitätskonstante (s) parallel zur Molekülachse kleiner ist als diejenige senkrecht zur Molekülachse. Die optische Anisotropie (An) einer Verbindung ist dann gross, wenn ihr Brechungsindex (n┴) senkrecht zur Molekülachse kleiner ist als ihr Brechungsindex (n") parailel zur Molekülachse; dieser optische Anisotropiewert, d.h. Δn=n"-n┴ wird hier als gering bezeichnet, wenn er kleiner als oder höchstens 0,2 (Δn≤0,2) ist. Geeignete Methoden zur Messung von Δn sind aus der Literatur (z.B. I. Haller etal. in "Mol. Cryst. and Liqu. Cryst." 16/1972/ 53-59) bekannt und werden meist auf eine bestimmte Lichtwellenlänge (hier 633 nm) bezogen.The anisotropic compounds known hitherto for liquid crystal mixtures, whose DK anisotropy, abbreviated to DKA or Δε, is negative, are mostly compounds composed of two or three aromatic rings with one or two carboxyl groups and optionally a covalent bond as bridges between the rings and with one or several side groups, that is to say nuclear substituents not located in the longitudinal axis of the molecule, such as nitrile or nitro groups, as described in particular in DE-B No. 2240864, DE-A Nos. 2613293, 2835662 and 2836086. However, these known anisotropic compounds with negative DKA (Δε) have high viscosity values and high values of the optical anisotropy (An); Δε = ε "-ε ┴ and Δn = n" -n ┴ , ie the DKA of a compound is negative if the dielectric constant (s) parallel to the molecular axis is smaller than that perpendicular to the molecular axis. The optical anisotropy (An) of a compound is large if its refractive index (n ┴ ) perpendicular to the molecular axis is smaller than its refractive index (n ") parallel to the molecular axis; this optical anisotropy value, ie Δn = n" -n ┴ is here called Designated low if it is less than or at most 0.2 (Δn≤0.2). Suitable methods for measuring Δn are known from the literature (for example I. Haller et al. In "Mol. Cryst. And Liqu. Cryst." 16/1972 / 53-59) and are usually based on a specific light wavelength (here 633 nm) based.

Aus der Literatur, z.B. der DE-A Nr. 2636684, ist es bekannt, dass sich die Viskosität von flüssigkristallinen und linearen, d.h. keine Seitengruppen aufweisenden aromatischen Verbindungen, wie Biphenylnitrilen, vermindern lässt, indem einer der Phenylenkerne durch einen Cyclohexanring ersetzt wird. Für die herstellung von für FK-Mischungen geeigneten anisotropen Verbindungen mit grosser negativer DK-Anisotropie und kleinen An-Werten wurde diese Möglichkeit bisher noch nicht genutzt.From the literature, e.g. DE-A No. 2636684, it is known that the viscosity of liquid crystalline and linear, i.e. aromatic compounds such as biphenylnitriles which have no side groups can be reduced by replacing one of the phenylene nuclei with a cyclohexane ring. So far, this possibility has not been used for the production of anisotropic compounds suitable for LC mixtures with large negative DK anisotropy and small An values.

Aus DE-A Nr. 2752975 sind schliesslich dreikernige anisotrope Verbindungen mit zwei oder mehr Esterbrücken und ein oder zwei Cyclohexylringen in der Grundstruktur des Moleküls bekannt, das gegebenenfalls eine Seitengruppe tragen kann. Die Viskosität der Grundstruktur ist aber wegen der mindestens zweifach auftretenden Esterbrücke relativ hoch und die Seitengruppe gilt dabei nicht als kritisch. Anisotrope, d.h. enantiotropflüssigkristalline oder monotrope bzw. potentiell flüssigkristalline Verbindungen mit grosser negativer DK-Anisotropie und kleinen An-Werten werden aber, wie von der Anmelderin in der DE-C Nr. 2835863.6 beschrieben, für FK-Anzeigen benötigt, welche den sogenannten inversen Guest-Host-Effekt ausnützen; ferner werden anisotrope Verbindungen mit solchen Eigenschaften auch für bestimmte Typen von dynamischen Streuzellen benötigt. Die bisher bekannten anisotropen Verbindungen mit negativer DK-Anisotropie erfüllen die geforderten Bedingungen aber nicht oder nicht in befriedigendem Masse. Benötigt werden aber auch neue anisotrope Verbindungen mit positiver DKA und geringer optischer Anisotropie (Δn), z.B. für FK-Anzeigen mit Multiplexbetrieb. Ferner werden neue Verbindungen mit negativer oder positiver DKA, einer verringerten Viskosität und niedrigen y-Werten (γ=Δε/ε┴) benötigt.Finally, DE-A No. 2752975 discloses trinuclear anisotropic compounds with two or more ester bridges and one or two cyclohexyl rings in the basic structure of the molecule, which can optionally carry a side group. However, the viscosity of the basic structure is relatively high because of the ester bridge which occurs at least twice and the side group is not considered critical. However, as described by the applicant in DE-C No. 2835863.6, anisotropic, ie enantiotropic or monotropic or potentially liquid-crystalline compounds with a large negative DK anisotropy and small An values are required for LC displays which display the so-called inverse guest -Use host effect; furthermore, anisotropic compounds with such properties are also required for certain types of dynamic scatter cells. However, the previously known anisotropic compounds with negative DK anisotropy do not meet the required conditions or do so to a satisfactory extent. However, new anisotropic compounds with positive DKA and low optical anisotropy (Δn) are also required, for example for LC displays with multiplex operation. Furthermore, new compounds with negative or positive DKA, a reduced viscosity and low y values (γ = Δε / ε ┴ ) are required.

Aufgabe der Erfindung ist es daher, eine neue Gruppe von anisotropen Verbindungen mit negativer oder positiver DKA, geringer optischer Anisotropie, niedrigen y-Werten und verminderter Viskosität anzugeben.The object of the invention is therefore to provide a new group of anisotropic compounds with negative or positive DKA, low optical anisotropy, low y values and reduced viscosity.

Diese Aufgabe wird erfindungsgemäss gelöst durch anisotrope Verbindungen der Formel (1)

Figure imgb0001
in der die Flügelgruppen R1 und R2 Wasserstoff, C1 bis C12-Alkylgruppen oder C1 bis C12-Alkoxygruppen sind, und eine der Gruppen R1 und R2 ausserdem einen cyclischen Rest der Formel (1a) oder (1 b)
Figure imgb0002
darstellen kann; die Brücken Z1, Z2 und Z3 bedeuten einfache Kovalenzbindungen oder Carboxyl- oder Oxycarbonylgruppen, wobei aber höchstens eine der Gruppen Z1, Z2, Z3 Carboxyl bzw. Oxycarbonyl darstellt; R3 ist Wasserstoff, C1 bis C12-Alkyl oder C1 bis C12-Alkoxy; von den Seitengruppen X1 bis X4 bedeutet mindestens eine Halogen, Nitril oder Nitro. Als Verbindungen mit negativer bzw. stark negativer DKA werden Verbindungen (1) bevorzugt, bei welchen zwei oder mehr der Seitengruppen X1 bis X4 Halogen, Nitro oder Nitril sind, wobei Nitril bevorzugt wird.According to the invention, this object is achieved by anisotropic compounds of the formula (1)
Figure imgb0001
 in which the wing groups R 1 and R 2 are hydrogen, C 1 to C 12 alkyl groups or C 1 to C 12 alkoxy groups, and one of the groups R 1 and R 2 also a cyclic radical of the formula (1a) or (1 b )
Figure imgb0002
 can represent; the bridges Z 1 , Z 2 and Z 3 represent simple covalent bonds or carboxyl or oxycarbonyl groups, but at most one of the groups Z 1 , Z 2 , Z 3 represents carboxyl or oxycarbonyl; R 3 is hydrogen, C 1 to C 12 alkyl or C 1 to C 12 alkoxy; of the side groups X 1 to X 4 means at least one halogen, nitrile or nitro. Compounds (1) in which two or more of the side groups X 1 to X 4 are halogen, nitro or nitrile are preferred as compounds with negative or strongly negative DKA, with nitrile being preferred.

Beispiele für Halogen sind Chlor, Fluor, Brom und Jod. Es ist aber nicht erforderlich, dass alle X1 bis X4 als Seitengruppen wirken; dementsprechend können bis zu drei der Gruppen X1 bis X4, vorzugsweise bis zu zwei der Gruppen X1 bis X4, auch Wasserstoffatome darstellen.Examples of halogen are chlorine, fluorine, bromine and iodine. However, it is not necessary that all X 1 to X 4 act as side groups; accordingly up to three of the groups X 1 to X 4 , preferably up to two of the groups X 1 to X 4 , can also represent hydrogen atoms.

Verbindungen (1 ) mit mehr als einer Estergruppe im Molekül werden nicht beansprucht.Compounds (1) with more than one ester group in the molecule are not claimed.

Die erfindungsgemässen Verbindungen der Formel (1) werden im folgenden kurz auch als Verbindungen (1 ) bezeichnet.The compounds of the formula (1) according to the invention are also referred to below as compounds (1).

Bevorzugte Gruppen der Verbindungen (1 ) entsprechen den folgenden Formeln (2) bis (6):

Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
 Preferred groups of the compounds (1) correspond to the following formulas (2) to (6):
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007

In den obigen Formeln (2) bis (6) bedeuten:

  • R4 und R5 Wasserstoff oder/und C1 bis C12-Alkyl oder/und C1 bis C12-Alkoxy, und
  • R6 und R' C1 bis C12-Alkyl oder/und C1 bis C12-Alkoxy.
In the above formulas (2) to (6) mean:
  • R 4 and R 5 are hydrogen or / and C 1 to C 12 alkyl or / and C 1 to C 12 alkoxy, and
  • R 6 and R 'are C 1 to C 12 alkyl or / and C 1 to C 12 alkoxy.

In allen Formeln (2) bis (6) sind für Verbindungen mit negativer DKA vorzugsweise mindestens zwei der Gruppen X1 bis X4 Halogen (vorzugsweise Chlor), Nitro oder Nitril, wobei Nitrilgruppen besonders bevorzugt werden. Gemäss einer ebenfalls bevorzugten Ausführungsform trägt einer der Benzolkerne der Verbindungen der Formeln (2) bis (6) zwei Halogenatome, Nitrogruppen oder (bevorzugt) Nitrilgruppen.In all formulas (2) to (6), for compounds with a negative DKA, at least two of the groups X 1 to X 4 are preferably halogen (preferably chlorine), nitro or nitrile, nitrile groups being particularly preferred. According to a likewise preferred embodiment, one of the benzene nuclei of the compounds of the formulas (2) to (6) carries two halogen atoms, nitro groups or (preferably) nitrile groups.

Vorzugsweise ist ferner in den Formeln (2) bis (5) eine der Brücken Z2, Z3 Carboxyl (-COO-) oder Oxycarbonyl (-OOC-) und die andere eine einfache Kovalenzbindung.Also preferred in formulas (2) to (5) is one of the bridges Z 2 , Z 3 carboxyl (-COO-) or oxycarbonyl (-OOC-) and the other is a simple covalent bond.

Die Verbindungen (1) können nach an sich bekannten Methoden erhalten werden, z.B. durch Kondensation von entsprechenden Phenolen bzw. Cyclohexanolen mit den entsprechenden Benzoesäure- bzw. Cyclohexancarbonsäureverbindungen, wobei die jeweilige Säurekomponente vorzugsweise in Form eines entsprechend reaktionsfähigen funktionellen Säurederivates, z.B. eines Säurehalogenides, insbesondere des Säurechlorides, eingesetzt und die Umsetzung in einer flüssigen organischen Base, wie Pyridin, durchgeführt wird. Spezielle Beispiele werden weiter unten gegeben.The compounds (1) can be obtained by methods known per se, e.g. by condensation of corresponding phenols or cyclohexanols with the corresponding benzoic acid or cyclohexanecarboxylic acid compounds, the respective acid component preferably in the form of a correspondingly reactive functional acid derivative, e.g. of an acid halide, in particular acid chloride, and the reaction is carried out in a liquid organic base, such as pyridine. Specific examples are given below.

Erfindungsgemässe FK-Mischungen enthalten als Komponente eine Verbindung (1), z.B. in Anteilen von 1 bis 40 Gew.-%, oder mehrere unterschiedliche Verbindungen (1) in einem gewünschtenfalls auch höheren Gesamtanteil. FK-Mischungen, die als Komponente mindestens eine Verbindung der obigen Formeln (2) bis (6) enthalten, werden bevorzugt.LC mixtures according to the invention contain a component (1), e.g. in proportions of 1 to 40% by weight, or several different compounds (1) in a higher total proportion if desired. LC mixtures containing at least one compound of the above formulas (2) to (6) as a component are preferred.

Die Erfindung wird anhand der folgenden speziellen Beispiele weiter erläutert.The invention is further illustrated by the following specific examples.

Beispiel 1example 1

Herstellung von 2-Cyano-4-n-butylphenyl-(4"-n-pentyl-trans-cyclohexyl-4')-trans-cyclohexanoat (Formel 2; R4=n-C5H11-, Z2=―, Z3=-COO-, X1=-CN, R5=n-C4H9-)Preparation of 2-cyano-4-n-butylphenyl- (4 "-n-pentyl-trans-cyclohexyl-4 ') - trans-cyclohexanoate (formula 2; R 4 = nC 5 H 11 -, Z 2 = -, Z 3 = -COO-, X 1 = -CN, R 5 = nC 4 H 9 -)

4-trans-(4'-trans-n-Pentylcyclohexyl)cyclohexancarbonsäure (7 g, 25 mmol) wurde mitThionylchlorid (40 ml) 30 min auf Rückflusstemperatur erwärmt. Das entstandene Säurechlorid wurde vom überschüssigen Thionylchlorid befreit. Dasso gewonnene Säurechlorid wurde nun zu einer Lösung von 2-Cyano-4-n-butylphenol (4,5 g, 25 mmol) in 100 ml Pyridin bei 0° C zugetropft. Nach Beendigung der Reaktion wurde das Gemisch in überschüssige verdünnte Salzsäure gegossen und mit Methylenchlorid extrahiert. Das aus dem Extrakt durch Eindampfen erhaltene Rohprodukt wurde aus Hexan umkristallisiert, Die so erhaltene Zielverbindung dieses Beispiels ist nematisch-enantiotrop (Tm=66,1°C, Tc=157,8°C) und hat eine negative DK-Anisotropie sowie ein Δn ≤ 0,2.4-trans- (4'-trans-n-pentylcyclohexyl) cyclohexane carboxylic acid (7 g, 25 mmol) was warmed to reflux temperature with thionyl chloride (40 ml) for 30 min. The resulting acid chloride was freed from the excess thionyl chloride. The acid chloride thus obtained was then added dropwise to a solution of 2-cyano-4-n-butylphenol (4.5 g, 25 mmol) in 100 ml of pyridine at 0 ° C. After the reaction was completed, the mixture was poured into excess dilute hydrochloric acid and extracted with methylene chloride. The crude product obtained from the extract by evaporation was recrystallized from hexane. The target compound obtained in this example is nematic-enantiotropic (T m = 66.1 ° C, T c = 157.8 ° C) and has a negative DK anisotropy as well a Δn ≤ 0.2.

Beispiel 2Example 2

Herstellung von 2,3-Dichloro-4-n-pentylphenyl-(4"-n-pentyl-trans-cyclohexyl-4')-trans-cyclohexanoat (Formel 2; R4=n-C5H11, Z2=―, Z3=-COO-, X' =CI, X2=Cl, R5=n-C5H11)Preparation of 2,3-dichloro-4-n-pentylphenyl- (4 "-n-pentyl-trans-cyclohexyl-4 ') - trans-cyclohexanoate (formula 2; R 4 = nC 5 H 11 , Z 2 = -, Z 3 = -COO-, X '= CI, X 2 = Cl, R 5 = nC 5 H 11 )

4-trans-(4'-trans-n-Pentylcyclohexyl)cyclohexancarbonsäure (10 g, 36,5 mmol) wurde mit Thionylchlorid (50 ml) 1 h unter Rückfluss gekocht. Das überschüssige Thionylchlorid wurde destilliert. Das entstandene Säurechlorid wurde zu einer Lösung von 5,3 g (36,5 mmol) 2,3-Dichlor-4-n-pentylphenol (Kp. 85°C/0,007 Torr) in 100 ml Pyridin zugetropft. Die Reaktionsmischung wurde über Nacht gerührt und dann auf verdünnte Salzsäure gegossen. Das Produkt wurde mit Methylenchlorid extrahiert. Zur Reinigung wurde das Produkt aus Hexan umkristallisiert. Sie zeigt eine enantiotrope nematische Phase (Tm=40° C, Tc= 180° C) und hat eine negative DK-Anisotropie sowie ein An ≤0,2.4-trans- (4'-trans-n-pentylcyclohexyl) cyclohexane carboxylic acid (10 g, 36.5 mmol) was refluxed with thionyl chloride (50 ml) for 1 h. The excess thionyl chloride was distilled. The acid chloride formed was added dropwise to a solution of 5.3 g (36.5 mmol) of 2,3-dichloro-4-n-pentylphenol (bp. 85 ° C / 0.007 Torr) in 100 ml of pyridine. The reaction mixture was stirred overnight and then poured onto dilute hydrochloric acid. The product was extracted with methylene chloride. The product was recrystallized from hexane for purification. It shows an enantiotropic nematic phase (T m = 40 ° C, T c = 180 ° C) and has a negative DK anisotropy and an An ≤0.2.

Beispiel 3Example 3

Herstellung von 2,3-Dicyano-4-n-pentylphenyl-(4"-n-pentyl-trans-cyclohexyl-4')-trans-cyclohexanoat (Formel 2; R4=n-C5H11, Z2=―, Z3=-COO-, X1=CN, X2=CN, R5=n-C5H11)Preparation of 2,3-dicyano-4-n-pentylphenyl- (4 "-n-pentyl-trans-cyclohexyl-4 ') - trans-cyclohexanoate (formula 2; R 4 = nC 5 H 11 , Z 2 = -, Z 3 = -COO-, X 1 = CN, X 2 = CN, R 5 = nC 5 H 11 )

Nach der in Beispiel 2 beschriebenen Arbeitsweise wurde die Zielverbindung des vorliegenden Beispiels in analoger Weise aus äquimolaren (36,5 mmol) Mengen der in Beispiel 2 angegebenen Cyclohexancarbonsäureverbindung - wiederum unter Umwandlung derselben mit Thionylchlorid in das entsprechende Säurechlorid - und 2,3-Dicyano-4-n-pentylphenol (anstelle des entsprechenden Dichlorophenols von Beispiel 2) und Aufarbeitung wie oben hergestellt. Die so erhaltene Zielverbindung ist ebenfalls nematisch-enantiotrop und hat eine negative DK-Anisotropie sowie ein An ≤0,2.According to the procedure described in Example 2, the target compound of the present example was obtained in an analogous manner from equimolar (36.5 mmol) amounts of the cyclohexane carboxylic acid compound given in Example 2 - again by converting the same with thionyl chloride into the corresponding acid chloride - and 2,3-dicyano-4-n-pentylphenol (instead of the corresponding dichlorophenol from Example 2) and workup prepared as above. The target compound thus obtained is also nematic-enantiotropic and has a negative DK anisotropy and an An ≤0.2.

Beispiel 4Example 4

Herstellung von 2-Cyano-4-n-butylphenyl-(4"-n-pentyl-trans-cyclohexyl-4') -benzoat (Formel 4; R4=n-C5H11, Z2=―, Z3=-COO-, X1 =X2=X4=H, X3=CN, R5=n-C4H9)Preparation of 2-cyano-4-n-butylphenyl- (4 "-n-pentyl-trans-cyclohexyl-4 ') benzoate (Formula 4; R 4 = nC 5 H 11 , Z 2 = -, Z 3 = - COO-, X 1 = X 2 = X 4 = H, X 3 = CN, R 5 = nC 4 H 9 )

4-(4'-trans-n-Pentylcyclohexyl)benzoesäure (10 g, 36,5 mmol) wurde mit Thionylchlorid (50 ml) 1 h unter Rückfluss gekocht. Das entstandene Säurechlorid wurde von überschüssigem Thionylchlorid befreit. Das Säurechlorid wurde zu einer Lösung von 6,3 g (36,5 mmol) 2-Cyano-4-n-butylphenol in 100 ml Pyridin zugetropft. Nach Beendigung der Reaktion wurde das Gemisch in überschüssige verdünnte Salzsäure gegossen und mit Methylenchlorid extrahiert.4- (4'-trans-n-pentylcyclohexyl) benzoic acid (10 g, 36.5 mmol) was refluxed with thionyl chloride (50 ml) for 1 h. The resulting acid chloride was freed from excess thionyl chloride. The acid chloride was added dropwise to a solution of 6.3 g (36.5 mmol) of 2-cyano-4-n-butylphenol in 100 ml of pyridine. After the reaction was completed, the mixture was poured into excess dilute hydrochloric acid and extracted with methylene chloride.

Das Produkt wurde aus der organischen Phase durch Eindampfen des Lösungsmittels erhalten. Zur Reinigung wurde das Rohprodukt aus Äthanol umkristallisiert. Die erhaltene Verbindung ist nematisch-flüssigkristallin (Tm=49,5° C, Tc= 115,5°C) und hat eine negative DK-Anisotropie sowie ein Δn ≤0,2.The product was obtained from the organic phase by evaporating the solvent. The crude product was recrystallized from ethanol for purification. The compound obtained is nematic-liquid-crystalline (T m = 49.5 ° C, T c = 115.5 ° C) and has a negative DK anisotropy and a Δn ≤0.2.

Beispiele 5 bis 22Examples 5 to 22

In ähnlicher Weise wie oben wurden die folgenden erfindungsgemässen anisotropen und eine negative DK-Anisotropie aufweisenden Verbindungen (1) hergestellt. Die Cyclohexylringe sind jeweils in trans-Konfiguration; An ≤0,2:

  • 5: 2,3-Dicyano-4-propylphenyl-(4"-propyl-p-phenyfen-4')-cyclohexanoat
  • 6: 2,3-Dicyano-4-propylphenyl-(4"-pentyl-p-phenylen-4')-cyclohexanoat
  • 7: 2,3-Dicyano-4-propylphenyl-(2",3"-di- cyano-4"-propyl-p-phenylen-4')-cyclohexanoat
  • 8: 2,3-Dicyano-4-propylphenyl-(3"-cyano-4"-propyt-p-phenylen-4')-cyclohexanoat
  • 9: 2,3-Dichloro-4-pentylphenyl-(4"-propyl- p-phenylen-4')-cyclohexanoat
  • 10: 2,3-Dichloro-4-pentylphenyl- (3"-cyano-4"-propyl-p-phenylen-4') -cyclohexanoat
  • 11: 2,3-Dicyano-4-propylphenyl-(4"-pentyl- cyclohexyl-4')-cyclohexanoat
  • 12: 2,3-Dicyano-4-pentylphenyl-(4"-pentyl- cyclohexyl-4') -cyclohexanoat
  • 13: 2,3-Dichloro-4-propylphenyl-(4"-pentyl- cyctohexy)-4') -cyclohexanoat
  • 14:2-Cyano-4-propylphenyl-(4"-pentylcyclo- hexyl-4') -cyclohexanoat
  • 15: 2-Cyano-4-pentylphenyl-(4"-pentylcyclo- hexyt-4')-cyclohexanoat
  • 16: 2-Chtoro-4-pentylphenyl-(4"-pentyl- cyctohexyl-4')-cyclohexanoat
  • 17: 2-Nitro-4-pentylphenyl-(4"-pentylcyclo- hexyl-4') -cyclohexanoat
  • 18:2-Cyano-4-propylphenyl-(4"-pentylcyclo- hexyl-4')-benzoat
  • 19: 2-Cyano-4-pentylphenyl-(4"-pentylcyclo- hexyl-4')-benzoat
  • 20:2-Cyano-4-propylphenyl-(4"-pentylcyclo- hexyl-4') -2'-cyanobenzoat
  • 21:2-Cyano-4-propylphenyl-(4"-pentylcyclo- hexyl-4') -3'-cyanobenzoat
  • 22:2-Cyano-4-propylphenyl-(3"-cyano-4"- pentylphenylen-4')-cyclohexanoat.
The following anisotropic and negative DK anisotropy compounds (1) according to the invention were prepared in a similar manner as above. The cyclohexyl rings are each in the trans configuration; At ≤0.2:
  • 5: 2,3-dicyano-4-propylphenyl- (4 "-propyl-p-phenyfen-4 ') cyclohexanoate
  • 6: 2,3-dicyano-4-propylphenyl- (4 "-pentyl-p-phenylene-4 ') cyclohexanoate
  • 7: 2,3-dicyano-4-propylphenyl- (2 ", 3" -dicyano-4 "-propyl-p-phenylene-4 ') cyclohexanoate
  • 8: 2,3-dicyano-4-propylphenyl- (3 "-cyano-4" -propyt-p-phenylene-4 ') cyclohexanoate
  • 9: 2,3-dichloro-4-pentylphenyl- (4 "-propyl-p-phenylene-4 ') cyclohexanoate
  • 10: 2,3-dichloro-4-pentylphenyl- (3 "-cyano-4" -propyl-p-phenylene-4 ') cyclohexanoate
  • 11: 2,3-dicyano-4-propylphenyl- (4 "-pentyl-cyclohexyl-4 ') cyclohexanoate
  • 12: 2,3-dicyano-4-pentylphenyl- (4 "-pentyl-cyclohexyl-4 ') -cyclohexanoate
  • 13: 2,3-dichloro-4-propylphenyl- (4 "-pentyl-cyctohexy) -4 ') -cyclohexanoate
  • 14: 2-Cyano-4-propylphenyl- (4 "-pentylcyclo-hexyl-4 ') -cyclohexanoate
  • 15: 2-cyano-4-pentylphenyl- (4 "-pentylcyclohexyte-4 ') cyclohexanoate
  • 16: 2-Chtoro-4-pentylphenyl- (4 "-pentyl-cyctohexyl-4 ') cyclohexanoate
  • 17: 2-nitro-4-pentylphenyl- (4 "-pentylcyclohexyl-4 ') cyclohexanoate
  • 18: 2-cyano-4-propylphenyl- (4 "-pentylcyclo-hexyl-4 ') benzoate
  • 19: 2-Cyano-4-pentylphenyl- (4 "-pentylcyclohexyl-4 ') benzoate
  • 20: 2-Cyano-4-propylphenyl- (4 "-pentylcyclo-hexyl-4 ') -2'-cyanobenzoate
  • 21: 2-Cyano-4-propylphenyl- (4 "-pentylcyclo-hexyl-4 ') -3'-cyanobenzoate
  • 22: 2-cyano-4-propylphenyl- (3 "-cyano-4" - pentylphenylene-4 ') cyclohexanoate.

Beispiele 23 bis 44Examples 23 to 44

Auch die folgenden erfindungsgemässen Verbindungen der obigen Formel (6) sind anisotrop und zeigen eine negative Anisotropie und ein Δn ≤ 0,2:

  • 23: 4-Propylcyclohexyl-4'-propyl-2',3'-di- cyanobenzoat
  • 24: 4-Propylcyclohexyl-4'-pentyl-2',3'-di- cyanobenzoat
  • 25: 2,3-Dicyano-4-propylphenyl-4'-heptyl- cyclohexanoat
  • 26: 2,3-Dicyano-4-pentylphenyl-4'-propyl- cyclohexanoat
  • 27: 2,3-Dicyano-4-pentylphenyl-4'-pentyl- cyclohexanoat
  • 28: 2,3-Dicyano-4-propyloxyphenyl-4'-propylcyclohexanoat
  • 29: 2,3-Dicyano-4-propyloxyphenyl-4'-pentylcyclohexanoat
  • 30: 2,3-Dicyano-4-pentyloxyphenyl-4'-propylcyclohexanoat
  • 31: 2,3-Dichloro-4-pentyloxyphenyl-4'-pentylcyclohexanoat
  • 32: 2,3-Dichloro-4-propylphenyl-4'-propyl- oxycyclohexanoat
  • 33: 2,3-Dibromo-4-pentylphenyl-4'-propoxy- cyclohexanoat
  • 34: 2,3-Dinitro-4-pentylphenyl-4'-pentyl- oxycyclohexanoat
  • 35: 2,3-Dicyano-4-propylphenyl-4'-propyl- cyclohexan
  • 36: 2,3-Dicyano-4-propylphenyl-4'-pentyl- cyclohexan
  • 37: 2,3-Dicyano-4-propylphenyl-4'-heptyl- cyclohexan
  • 38: 2,3-Dicyano-4-pentyloxyphenyl-4'-propoxycyclohexan
  • 39: 2,3-Dicyano-4-pentyloxyphenyl-4'-pentyloxycyclohexan
  • 40: 2,3-Dicyano-4-propylphenyl-4'-butoxy- cyclohexan
  • 41: 2,3-Dichloro-4-pentylphenyl-4'-propyl- cyclohexan
  • 42: 2,3-Dinitro-4-heptylphenyl-4'-propyl- cyclohexan
  • 43: 2,3-Dichloro-4-pentylphenyl-4'-butoxy- cyclohexan
  • 44: 2,3-Dinitro-4-pentylphenyl-4'-butoxy- cyclohexan
The following compounds of formula (6) according to the invention are also anisotropic and show a negative anisotropy and a Δn ≤ 0.2:
  • 23: 4-propylcyclohexyl-4'-propyl-2 ', 3'-di-cyanobenzoate
  • 24: 4-Propylcyclohexyl-4'-pentyl-2 ', 3'-di-cyanobenzoate
  • 25: 2,3-dicyano-4-propylphenyl 4'-heptyl cyclohexanoate
  • 26: 2,3-dicyano-4-pentylphenyl-4'-propylcyclohexanoate
  • 27: 2,3-dicyano-4-pentylphenyl-4'-pentylcyclohexanoate
  • 28: 2,3-dicyano-4-propyloxyphenyl-4'-propylcyclohexanoate
  • 29: 2,3-dicyano-4-propyloxyphenyl-4'-pentylcyclohexanoate
  • 30: 2,3-dicyano-4-pentyloxyphenyl-4'-propylcyclohexanoate
  • 31: 2,3-dichloro-4-pentyloxyphenyl-4'-pentylcyclohexanoate
  • 32: 2,3-dichloro-4-propylphenyl-4'-propyloxycyclohexanoate
  • 33: 2,3-dibromo-4-pentylphenyl-4'-propoxycyclohexanoate
  • 34: 2,3-Dinitro-4-pentylphenyl-4'-pentyloxycyclohexanoate
  • 35: 2,3-dicyano-4-propylphenyl-4'-propylcyclohexane
  • 36: 2,3-dicyano-4-propylphenyl-4'-pentylcyclohexane
  • 37: 2,3-dicyano-4-propylphenyl-4'-heptylcyclohexane
  • 38: 2,3-dicyano-4-pentyloxyphenyl-4'-propoxycyclohexane
  • 39: 2,3-dicyano-4-pentyloxyphenyl-4'-pentyloxycyclohexane
  • 40: 2,3-dicyano-4-propylphenyl-4'-butoxycyclohexane
  • 41: 2,3-dichloro-4-pentylphenyl-4'-propylcyclohexane
  • 42: 2,3-Dinitro-4-heptylphenyl-4'-propylcyclohexane
  • 43: 2,3-dichloro-4-pentylphenyl-4'-butoxycyclohexane
  • 44: 2,3-Dinitro-4-pentylphenyl-4'-butoxycyclohexane

Alle Verbindungen der Beispiele 1 bis 44 haben ausser einer negativen DK-Anisotropie auch vorteilhaft niedrige Δn-Werte ≤0,2 und die Cyclohexanringe liegen jeweils in trans-Konfiguration vor. Die erfindungsgemässen Verbindungen (1) haben den überraschenden zusätzlichen Vorteil, dass ihre y-Werte (γ=Δε/ε┴) klein sind und häufig höchstens etwa 2 betragen, d.h. y ≤2.In addition to a negative DK anisotropy, all of the compounds in Examples 1 to 44 also advantageously have low Δn values 0 0.2 and the cyclohexane rings are each in a trans configuration. The compounds (1) according to the invention have the surprising additional advantage that their y values (γ = Δε / ε ┴ ) are small and often amount to at most about 2, ie y ≤2.

Claims (16)

1. An anisotropic compound with negative or positive DC-anisotropy and an optical anisotropy An ≤0.2, having the formula (1)
Figure imgb0036
in which R1 and R2 are independently hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or one of R1 and R2 can represent a cyclical fragment of the formula (1a) or (1 b)
Figure imgb0037
the bridges Z1, Z2 and Z3 are identical or different and are covalent bonds, carboxyl or oxycarbonyl groups, R3 is hydrogen, alkyl of 1 to 12 carbon atoms or alkoxy of 1 to 12 carbon atoms, and X1 to X4 are independently hydrogen, halogen, nitrile or nitro, wherein at least one of X1 to X4 is not hydrogen and at most one of the bridges Z1, Z2 and Z3 is a carboxyl or oxycarbonyl group.
2. The compound of claim 1, having the formula (2)
Figure imgb0038
wherein R4 and R5 are hydrogen, alkyl or alkoxy groups having 1 to 12 carbon atoms, respectively.
3. The compound of claim 1, having the formula (3)
Figure imgb0039
wherein R4 and R5 are hydrogen, alkyl or alkoxy groups having 1 to 12 carbon atoms, respectively, and X1 and X2 are not hydrogen when Z2 is a carboxyl group.
4. The compound of claim 1, having the formula (4)
Figure imgb0040
wherein R4 and R5 are hydrogen, alkyl or alkoxy groups having 1 to 12 carbon atoms, respectively, and at least two of the groups X1 to X4 are not hydrogen when Z2 is carboxyl.
5. The compound of claim 1, having the formula (5)
Figure imgb0041
wherein R4 and R5 are hydrogen, alkyl or alkoxy groups having 1 to 12 carbon atoms, respectively.
6. The compound of claim 1, having the formula (6)
Figure imgb0042
wherein R6 and R7 are alkyl or alkoxy groups having 1 to 12 carbon atoms, respectively.
7. The compound of claim 1, 2, 3, 4, 5 or 6, wherein both X1 and X2 are halogen, nitro or preferably nitrile.
8. The compound of claim 1, 2, 3, 4 or 5, wherein at least two of the groups X1 to X4 are halogen, nitro or preferably nitrile.
9. A liquid crystal composition which comprises as components at least one anisotropic compound with negative or positive DC-anisotropy and an optical anisotropy An ≤0.2, wherein the anisotropic compound is a compound having the formula (1)
Figure imgb0043
wherein R1 and R2 are independently hydrogen, alkyl having 1 to 12 cabon atoms, alkoxy having 1 to 12 carbon atoms, or one of R1 and R2 can represent a cyclical fragment of the formula (1a) or (1 b)
Figure imgb0044
the bridges Z1, Z2 and Z3 are identical or different and are covalent bonds, carboxyl or oxycarbonyl groups, R3 is hydrogen, alkyl of 1 to 12 carbon atoms or alkoxy of 1 to 12 carbon atoms, and X1 to X4 are independently hydrogen, halogen, nitrile or nitro, wherein at least one of X1 to X4 is not hydrogen and at most one of the bridges Z1, Z2 and Z3 is a carboxyl or oxycarbonyl group.
10. The liquid crystal composition of claim 9, wherein the anisotropic compound has the formula (2)
Figure imgb0045
wherein R4 and R5 are hydrogen, alkyl or alkoxy having 1 to 12 carbon atoms, respectively.
11. The liquid crystal composition of claim 9, wherein the anisotropic compound has the formula (3)
Figure imgb0046
wherein R4 and R5 are hydrogen, alkyl or alkoxy having 1 to 12 carbon atoms, respectively, and X1 and X2 are not hydrogen when Z2 is a carboxyl group.
12. The liquid crystal composition of claim 9, wherein the anisotropic compound has the formula (4)
Figure imgb0047
wherein R4 and R5 are hydrogen, alkyl or alkoxy having 1 to 12 carbon atoms, respectively, and at least two of X1 to X4 are not hydrogen when R2 is carboxyl.
13. The liquid crystal composition of claim 9, wherein the anisotropic compound has the formula (5)
Figure imgb0048
wherein R4 and R5 are hyrogen, alkyl or alkoxy having 1 to 12 carbon atoms, respectively.
14. The liquid crystal composition of claim 9, wherein the anisotropic compound has the formula (6)
Figure imgb0049
wherein R6 and R7 are alkyl or alkoxy having 1 to 12 carbon atoms, respectively.
15. The liquid crystal composition of claim 9, 10, 11, 12, 13 or 14, wherein both X1 and X2 are halogen, nitro or preferably nitrile.
16. The liquid crystal composition of claim 9, 10, 11, 12 or 13, wherein at least two of X1 to X4 are halogen, nitro or preferably nitrile.
EP80200464A 1979-07-18 1980-05-19 Anisotropic compounds with negative or positive direct anisotropy and limited optical anisotropy, and liquid crystal mixtures containing them Expired EP0023728B1 (en)

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EP0023728A1 (en) 1981-02-11
US4368135A (en) 1983-01-11
DE3064522D1 (en) 1983-09-15

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